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The research described in this thesis was designed to yield information on the impact of particle-bound pesticides on organisms living in the interface between sediment and water column in a temporarily open estuary (TOCEs). It was hypothesized that natural variables such as salinity and temperature and anthropogenic stressors such as particle-bound pesticides contribute to the variability of the system. A multiple line of evidence approach is necessary due to the variability in sediment type, contaminant distribution and spatial and temporal variability within the ecosystem in particular within TOCEs. The first aim of this thesis was to identify which particle-bound pesticides are important to the contamination of the Lourens River estuary (Western Cape, South Africa), taking into account their environmental concentrations, physico-chemical and toxicological properties (Exposure assessment). The second aim was to identify spatial and temporal variations in particle bound pesticide contamination, natural environmental variables and benthic community structure (effect assessment). The third aim was to test the hypothesis: "does adaptation to fluctuating salinities lead to enhanced survival of the harpacticoid copepod Mesochra parva when exposed to a combination of particle associated chlorpyrifos exposure and hypo-osmotic stress during a 96 h sediment toxicity test?" The last aim was to identify the driving environmental variables (including natural and anthropogenic stressors) in a "natural" (Rooiels River) compared to a "disturbed" (Lourens River) estuary and to identify if and how these variables change the benthic community structure in both estuaries. Data produced in this research thus provide important information to understand the impact of pesticides and its interaction with natural variables in a temporarily open estuary. To summarise, this study indicated, by the use of the multi-evidence approach, that the pesticides endosulfan and chlorpyrifos posed a risk towards benthic organisms in a temporarily open estuary in particular during spring season. Furthermore an important link between pesticide exposure/ toxicity and salinity was identified, which has important implications for the management of temporarily open estuaries.
Stream ecosystems are one of the most threatened ecosystems worldwide due to their exposure to diverse anthropogenic stressors. Pesticides appear to be the most relevant stressor for agricultural streams. Due to the current mismatch of modelled and measured pesticide concentrations, monitoring is necessary to inform risk assessment or improve future pesticide approvals. Knowing if biotic stress responses are similar across large scales and long time frames could ultimately help in estimating protective stressor thresholds.
This thesis starts with an overview of entry pathways of pesticides to streams as well as the framework of current pesticide monitoring and gives an outline of the objectives of the thesis. In chapter 2, routine monitoring data based on grab sampling from several countries is analysed to identify the most frequently occurring pesticide mixtures. These mixtures are comprised of relatively low numbers of pesticides, of which herbicides are dominating. The detected pesticide mixtures differ between regions and countries, due to differences in the spectrum of analysed compounds and limits of quantification. Current routine monitoring does not include sampling during pesticide peaks associated with heavy rainfall events which likely influences the detected pesticide mixtures. In chapter 3, sampling rates of 42 organic pesticides for passive sampling are provided together with recommendations for the monitoring of field-relevant peaks. Using this information, in chapter 4 a pesticide gradient is established in an Eastern European region where agricultural intensity adjacent to sampled streams ranges from low to high. In contrast to current routine monitoring, rainfall events were sampled and a magnitude of pesticides were analysed. This led to the simultaneous detection of numerous pesticides of which one to three drive the pesticide toxicity. The toxicity, however, showed no relationship to the agricultural intensity. Using microcosms, the stress responses of fungal communities, the hyphomycetes, and the related ecosystem function of leaf decomposition, is investigated in chapter 5. Effects of a field-relevant fungicide mixture are examined across three biogeographical regions for three consecutive cycles of microbial leaf colonisation and decomposition. Despite different initial communities, stress responses as well as recoveries were similar across biogeographical regions, indicating a general pattern.
Overall, this thesis contributes to an improved understanding of occurrence and concentrations of pesticides mixtures in streams, their monitoring and impact on an ecosystem function. We showed that estimated pesticide toxicities reach levels that affect non-target organisms and thereby potentially whole ecosystems. Routine monitoring, however, likely underestimates the threat by pesticides. Effects leading to a loss in biodiversity or functions in streams ecosystems can be reduced by reassessing approved pesticides with ongoing targeted monitoring and increased knowledge of effects caused by these pesticides.